Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
  • C09D11/104—Polyesters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/12—Polyester-amides

Definitions

• the present invention relates to a novel polymer blend useful in printing inks which contains a linear, water-dissipatable polyester or polyesteramide material in combination with an acrylic polymer.
• Inks containing a water-dissipatable polyester or polyesteramide are well known in the art (see, for example, U.S. Patents 4,704,309 and 4,738,785). Inks containing such a polymeric material have many desirable properties such as good adhesion to a variety of substrates and a wide viscosity range. However, despite the advantages obtained using such a polymeric material in aqueous inks, it is known that aqueous inks with such a polymer by itself have serious problems for many applications, namely poor water resistance and poor block resistance (e.g., see Japanese Kokai 57-10663). It would be highly desirable to have a material that imparts good water resistance and block resistance while maintaining the other advantages associated with the use of the water-dissipatable polyester or polyesteramide.
• the water-dissipatable polyester material as described herein when mixed with an acrylic polymer, will provide to ink compositions good water resistance and good block resistance without concomitant substantial sacrifice of the advantages obtained by use of the water-dissipatable polyester material alone.
• This polymer blend can be used to prepare water-based inks, ink overprints and ink primers, which shall be referred to herein collectively as "ink compositions.” More specifically, the present invention is directed to a polymer blend comprising:
• the present invention is also directed to an ink composition made from the polymer blend of this invention comprising:
• water-dissipatable polyester As used herein, the term "water-dissipatable polyester”, “water-dissipatable polyester material”, “polyester material”, or “polyester” refers to Component (A) described hereinabove and “acrylic polymer” refers to Component (B) described hereinabove, and “polymer blend” refers to a blend of Component (A) and Component (B).
• water-dissipatable or “water-dispersible”
• water-dispersible refers to the activity of a water or aqueous solution on the polymer. The term is specifically intended to cover those situations wherein the solution dissolves and/or disperses the polyester material therein and/or therethrough.
• an amount effective to increase the block resistance or water resistance properties of is meant that amount of acrylic polymer that, when added to the water-dissipatable polyester, will increase the block resistance and/or water resistance of an ink composition as compared to a comparable ink composition without said acrylic polymer. It is preferred that the water resistance of ink compositions made from the polymer blend of the present invention is at least good; more preferred is excellent.
• the ink compositions made from the polymer blend of the present invention do not block above about 100° F (37.78° C) ; more preferably do not block above about 120° to 220° F (48.89° to 104.44° C), for 5 seconds on a Sentinel Heat Sealer at 40 psi (275.79 kilopascal).
• Water resistance can be determined by the procedure described in Example 5.
• Block resistance can be determined by the procedure described in Example 7.
• compatible is meant that a 60/40 weight blend of acrylic/polyester polymer (or a blend with less acrylic polymer) will not gel or have a significant increase in viscosity after being held at 120°F (48.89°C) for 24 hours or at room temperature for 14 days.
• gel or “gelling” is meant that the blend is not pourable at room temperature.
• a significant viscosity increase after 24 hours at 120° F (48.89° C) is typically at least two or three times the viscosity at zero time.
• the acrylic polymers which are compatible at the higher acrylic concentrations of the acrylic/polyester blends are preferred.
• acrylic polymers that are compatible in acrylic concentrations up to a 60/40 weight blend of acrylic/polyester are preferred over acrylic polymers that are compatible only up to a 50/50 weight blend of acrylic/polyester.
• Preferred acrylic polymers are compatible at acrylic concentrations of at least 30/70 (weight blend of acrylic/polyester) (i.e., at least 30 weight percent acrylic polymer) and more preferred acrylic polymers are compatible at acrylic concentrations of at least 40/60 (i.e., at least 40 weight percent acrylic polymer).
• Component (B) is present in an amount effective to increase the block resistance or water resistance properties of Component (A) when formulated into an ink composition; Also preferably Component (B) is present in am amount of about 30 percent to 45 percent; and Component (A) is present in an amount of about 45 percent to 90 percent, more preferably 55 percent to 70 percent; these percentages being based on the total weight of Components (A) and (B).
• Component (I) is present in an amount of about 5 to 40 weight percent, that Component (II) is present in an amount of about 0 to 35 weight percent, and that Component III is present in an amount of about 35 to 95 weight percent.
• the ink composition is a finished ink, it is preferred that at least about 0.5 weight percent of colorant is present. More typically, in inks, at least about 5 weight percent of colorant is present.
• the ink composition contains an organic pigment, typically such an organic pigment is present in an amount of about 17.5 weight percent or less of the total composition.
• ink composition contains an inorganic pigment, typically such inorganic pigment is present in an amount of about 30 weight percent or less of the total composition.
• the ink compositions can optionally contain up to about 10 weight percent, preferably up to about 3 weight percent of one or more additives.
• additives include waxes such as Jonwax 26, Jonwax 120 (available from S. C. Johnson and Sons, Inc., Racine, Wisconsin 43403; U.S.A.), or Vanwax 35 (available from Vantage, Garfield, New Jersey 07026); surfactants such as Surfynol 104 and Surfonyl 440 (available from Air Products and Chemicals, Allentown, Pennsylvania 18105); modifiers (for example, defoamers) such as WBT-409, Resolv (available from Vantage), Carbowet 990 (available from Vantage), OT-70 aerosol (available from McIntyre, Chicago, Illinois 60632), Foamaster 111 (available from Henkel Corporation, Morristown, New Jersey 07960); alcohols such as n-propyl alcohol, isopropyl alcohol, propylene glycol, ethylene glycol monobutyl ether
• pH stabilizers it is desirable to add a small amount of one or more pH stabilizers to the ink compositions to keep the pH within a desired range. For example, it is common to add about 0.1 weight percent sodium acetate to an ink or aqueous solution/dispersion of polymer blend.
• the metallic portion of the metallic sulfonate group is preferably a monovalent metal such as Na + , K + , or Li +.
• the nonmetallic portion of the nonmetallic sulfonate group is a nitrogen-based cation derived from nitrogen-containing bases which may be aliphatic, cycloaliphatic or aromatic basic compounds that have ionization constants in water at 25° C of 10- 3 to 10- 10 , preferably 10- 5 to 10- 8 .
• nitrogen-containing bases are ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine.
• Such nitrogen-containing bases and cations derived therefrom are described in U.S. Patent 4,304,901, incorporated herein by reference.
• reactant (d) In the water-dissipatable polymer it is preferred that very minor, e.g., less than about 10 mol percent based on all reactants, of reactant (d) is employed, that at least about 70 mol percent of reactant (c) is glycol, and that at least about 70 mol percent of all the hydroxy equivalents is present in the glycol. It is also preferred that a substantial portion of reactant (c) is a cycloaliphaticdimethanol, e.g., up to 50 mole percent of a cycloaliphaticdimethanol such as 1,4-cylcohexanedimethanol.
• a cycloaliphaticdimethanol e.g., up to 50 mole percent of a cycloaliphaticdimethanol such as 1,4-cylcohexanedimethanol.
• the inherent viscosities (LV.) of the particular water-dissipatable polymeric material useful herein range from about 0.1 to about 1.0 determined according to ASTM D2857-70 procedure, in a Wagner Viscometer of Lab Glass, Inc., of Vineland, New Jersey, having a 1/2 mL capillary bulb, using a polymer concentration about 0.25% by weight in 60/40 by weight of phenol/tetrachloroethane. The procedure is carried out by heating the polymer/solvent system at 120°C for 15 minutes, cooling the solution to 25° C and measuring the time of flow at 25°C.
• the LV. is calculated from the equation where:
• the acrylic polymers useful in the present invention are commercially available and/or can be made using conventional techniques known in the art.
• the molecular weight of the acrylic polymer is at least about 10,000 and preferred is at least about 200,000.
• the acrylic polymer useful in the present invention has an acid number of about 200 or less; more preferred is less than about 55 and most preferred is less than about 50. It is also preferred that the glass transition temperature (Tg) of the acylic polymer is greater than -about 0.
• the acrylic polymer of the present invention preferably comprises repeating units of the formula: wherein R' is H, a straight, branched, or cyclic alkyl group of 1 to 20 carbon, preferably 1 to 10 carbon atoms, optionally substituted with up to 2 substituents such as C 1 -C S alkoxy or halogen such as chloro- or bromo; and R" is H or methyl.
• R' is H, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, hexyl, heptyl, 2-ethylhexyl, 2-ethylbutyl, dodecyl, hexadecyl, 2-ethoxyethyl, or cyclohexyl.
• the acrylic polymer can optionally be styrenated and therefore further comprise repeating units of the formula:
• the acrylic polymer can also be a copolymer containing repeating units derived from an acrylonitule monomer.
• the acrylic polymer can be blended with the polyester material in pure form or either or both polymers can be in a mixture with water or an aqueous solution.
• the mixture of the acrylic polymer and water or aqueous solution can be in the form of a water-borne alkali soluble resin, a colloidal dispersion, or emulsion.
• Preferred for use is an emulsion or dispersion of an acrylic polymer having a pH of about 7.5-9.0 and a Brookfield viscosity of about 200-1,000 centipoise (cp) at 25°C.
• cp centipoise
• an aqueous solution is used to make the aqueous emulsion or dispersion of acrylic polymer
• such solution will contain one or more additives typically used in the art in amounts of to about 5 weight percent of the emulsion, preferably about 1 to about 3 weight percent.
• additives can be emulsion stabilizers, surfactants, dispersants, antimicrobials or biocides, pH stabilizers, and the like.
• the additives described herein as suitable for use in the ink compositions are also suitable for use with the mixture of acrylic polymer and aqueous solution.
• Table 1 lists certain acrylic polymer emulsions (except for Joncryl 67 which is a solid or flake) commercially available and certain properties thereof.
• the acrylics having the tradename "Joncryt" are available from S. C. Johnson and Sons, Inc., Racine, Wisconsin 43403, U.S.A. and the acrylics having the tradename Vancryl are available from Vantage.
• polyester materials and/or two or more acrylic polymers can be used in the present invention.
• the water-dissipatable polymer can be made by known techniques, for example, by those disclosed in U.S. Patent 3,734,874; 3,779,993; and 4,233,196; the disclosures of which are incorporated herein by reference in their entirety.
• the aqueous solution or dispersion of water-dissipatable polyester to be blended with the acrylic polymer dispersion preferably comprises about 26 to 38 weight percent of polyester material with the remainder being water or an aqueous solution.
• the aqueous solution can be the same or be similar to the aqueous solution used to make the aqueous dispersion an emulsion of acrylic polymer, with the amount of additives being present in an amount of up to about 5 weight percent, preferably about 1 to about 3 weight percent.
• the ink compositions of this invention can be for any of the typical ink applications such as flexographic, gravure, letterpress, ink-jet, or screen-process printing applications.
• the ink compositions of the present invention have excellent adhesion to a wide variety of substrates including plastic films such as polyester, polyethylene or polypropylene; aluminum foil; glass; and paper.
• the ink compositions of the present invention should have a pH of about 8.2 or lower; preferred is a pH of about 7 to 8. If the pH is higher than about 8.2, there is a danger of the polymer(s) hydrolyzing which results in gelling of the system.
• the polyester material can be dispersed in water or aqueous solution using the techniques described herein or known in the art and then blended with an aqueous dispersion or emulsion of acrylic polymer prepared by similar techniques, or blended with an aqueous emulsion or dispersion of acrylic polymer in a form commercially available.
• the following procedure can be used for dispersing the polyester in water:
• the water should be preheated to about 180° F (82.22° C) to about 200° F (93.33° C) and the polyester in pellet form is added rapidly to the vortex under high shear stirring.
• a Cowless Dissolver, Waring Blender, or similar equipment may be used. Once the water is heated to the desired temperature, additional heat input is not required.
• dispersion of the pellets should be complete within 15 to 30 minutes stirring. Continued agitation with cooling may be desirable to prevent thickening at the surface due to water evaporation. Viscosities of the dispersions remain low up to polyester levels of 25 percent to 30 percent and viscosities increase sharply above these levels. Viscosities of the dispersions will be influenced by the degree of polymer dispersion obtained which is affected by the dispersing temperature, shear, and time.
• the polyester blend content typically may range from about 15 percent to about 50 percent by weight of the aqueous dispersion with the preferred for most applications being from about 26 percent to about 38 percent.
• the inks, overprints, and primers of this invention can be prepared, for example, as disclosed in U.S. Patent 4,148,779, which is incorporated herein by reference in its entirety.
• the printing ink, overprint, or primer may be prepared as follows: The colorant is added to the polymer blend dispersion and, at a properly adjusted viscosity, dispersed thereinto with ball mill, sand mill, high-shear fluid flow mill, Cowles Dissolver, Katy Mill or the like. The colorants.
• ink composition may be dispersed directly in the polymer by milling on a heated two-roll mill at about 220° to 360°F (104.44° to 182.22°C) and using processing aids as desired, such as solvents or plasticizers.
• processing aids such as solvents or plasticizers.
• the viscosity and printing characteristics of the ink composition may be modified further by addition of water, solvents, plasticizers, sequestered wax, surfactants and the like to suit the particular printing needs.
• the amounts and nature of these optional additives have been previously described herein.
• the present invention is not limited to any type of dye, pigment, filler, or the like, all of which are hereinafter included in the term "colorant,” and can accommodate any colorant which can be dispersed, milled, mixed, blended or dissolved in any manner in either the polymer blend, water or aqueous polymer system.
• Exemplary useful C.I. pigments for use in the present invention are given in the following table:
• ink compositions prepared from the above polymer blends may be superior over prior aqueous ink compositions in one or more of such properties as pigment wetting, pigment stability, temperature stability (heat and freeze-thaw), nonsettling for extended periods of time, nonpolluting with respect to odor and volatile organics, nonflocculating, long "open" time in the press fountain, wide viscosity range inks, adhesion to a variety of substrates, hardness, gloss, drying rate on substrates, film-forming properties at low temperatures without organic co-solvents, resistance to grease, water and scuff, compatibility with other water-based inks, wet rub resistance, ink mileage characteristics (considerable water dilution allowable at the press), ink press stability in general, printability (clean, sharp transfer without “stringing or misting"), trapping, easy clean up, nonplugging of printing plates, flexibility, redispersibility or rewetting, crinkle resistance, solvent resistance, alkali, chemical and
• the polymer obtained has an inherent viscosity (I.V.) of 0.36 and is tough and rubbery. It is dissipatable in hot water to the extent of about 29 weight percent to give a clear, slightly viscous solution.
• the composition of the acid moieties of this polyester material is analyzed to be 82 mole 0/ 0 isophthalic acid residue and 18 mole % 5-sodiosulfoisophthalic acid residue, and of the glycol moieties is analyzed to be 54 mole % diethylene glycol and 46 mole % 1,4-cyclohexanedimethanol.
• polyester polymer from Example 1 with stirring.
• the mixture is heated at 90° C for two hours with stirring.
• the dispersion is cooled to 75° C and 227.5 g of n-propyl alcohol is added dropwise with stirring.
• the dispersion is allowed to cool to 35°C with stirring and 13.65 g of Tekamer 38 AD (biocide) is added with stirring.
• the clear polyester dispersion has the following composition.
• the overprint varnishes are made by slowly adding Joncryl 77 (see Table 1) to the polyester dispersion of Example 2 with stirring.
• the amounts of each component used and the resulting weight percent of Joncryl 77 polymer ( 0 / 0 of total polymer solids) contained in the varnish is listed in Table 2. These varnishes are stirred for five minutes and then filtered through a cheese cloth.
• the varnishes are applied on Aluminum Foil and Polypropylene with a Number 3 and 6 Meyer rod and with a Gravure and Flexo Handproofer. These samples are then allowed to dry for 24 hours at 70° F(21.11°C), 60 0 / 0 relative humidity or dried in the oven at 100°C for 3 seconds.
• Example 3 The overprints of Example 3 are applied to aluminum foil as described in Example 4.
• the water resistance of the samples are determined by the water spot test. Water Spot Test - Distilled water drops were left on the film surface for 1, 5, and 20 minutes, then wiped off gently with a facial tissue. The integrity of the film is visually assessed.
• the water spot test is rated as follows:
• the test results for the overprint varnishes of Table 2 are shown in Table 3. At least 30% Joncryl 77 (total polymer solids) is required to obtain excellent water resistance. The water resistance can also be determined by a water soak test.
• An ink millbase was made by adding 100.0 g of blue pigment, PV Fast Blue B2G-A from Hoechst (Color Index Pigment Blue 15:3), 2.0 g of defoamer and 96.0 of water to 202.0 g of polyester dispersion (Example 2) or Joncryl 77 emulsion (Table 1). The mixture is then shaken with 400.0 g of glass beads for 4 hours on a paint shaker and is filtered through cheese cloth. To 50.0 g of the filterate is added with stirring 49.5 g of the polyester dispersion and/or the Joncryl 77 emulsion and 0.5 g of defoamer. Each ink contains 12.5% pigment, 0.75% defoamer, and varying percents of the polyester dispersion and Joncryl 77 emulsion as shown in Table 4, the percentages being by weight.
• overprint varnish and ink The preparation of the overprint varnish and ink is the same as in the above examples except Joncryl 87 (Table 1) is used instead of Joncryl 77.
• Joncryl 87 Table 1
• These overprint varnishes and inks have good water resistance at 30 weight percent or higher Joncryl 87 (weight percent of total polymer solids).
• the block resistance of these inks and overprints are determined as follows:
• the inks and overprint varnishes are applied to 60-pound (27.22 kilogram (kg)) paper label stock as described in Example 4.
• the printed samples were permitted to dry or age at 70° F (21.11°C) and 60% relative humidity for 24 hours.
• the samples containing 30% or higher Joncryl 87 (percent total polymer solids) did not block (face to face) at 140° to 180° F (60° to 82.2°C) for 5 seconds on Sentinel Heat Sealer at 40 psi (275.79 kilopascal), and had excellent water resistance.
• the compatibility test of the polymer blends in the ink composition is monitored by pH readings, viscosity change and observed gelling after aging the sample for 2 weeks in the oven at 120° F (48.89° C) and 4 weeks at room temperature, 70° F (21.11°C), and also after putting them in the freezer at -25° F (-31.67°C) for 24 hours (3 cycles).
• the results of one sample are in Table 6.
• Example 2 To 103.4 g of the polyester dispersion from Example 2 is added 100.0 g of water, 4.7 g of n-propyl alcohol, 61.9 g of Joncryl 74 (see Table 1), acrylic polymer emulsion, and 30.0 g of PV Fast Blue B2G-A from Hoechst (C.I. Pigment Blue 15:3) with stirring. To this mixture is added 4.2 g of Acrysol RM-825 (from Rohm and Haas). This mixture is circulated through an Eiger Mini Motor Mill (grinding media - ceramic beads) at 5,000 rpm for 5 minutes. The resulting had a viscosity of 17 seconds on a No. 2 Zahn cup. The composition of this ink is as follows.
• This 50/50 acrylic/polyester (% of total polymer solids) ink is applied on aluminum foil and a coated paper stock as described in Example 4.
• the water resistance of the room temperature dried samples is determined as described in Example 5.
• Excellent water resistance is obtained with this 50% solid Joncryl 74 (per total polymer solids) ink.
• the viscosity of this ink after one week at 120° F (48.89° C) is constant (17 seconds) on a No. 2 Zahn cup.
• Example 2 To 8.28 g of polyester dispersion of Example 2 is added 3.0 g of Joncryl 67 solution of Example 9, 0.75 g of Flexiverse Yellow YFD5100 (commercial pigment dispersion from Sun Chemical), 1.2 g of Flexiverse Red RFD4257, and 1.77 g of water with stirring.
• the Flexiverse dispersions are assumed to contain 8.75 weight percent of Joncryl 67 acrylic polymer.
• the resulting ink contains about 26% Joncryl 67 and 74% polyester (weight percent of total polymer) polymers.
• the ink is applied on aluminum foil as in Example 4 and allowed to dry overnight at room temperature. The water resistance of this ink is determined as described in Example 5. This ink has excellent water resistance. Excellent water resistance is obtained with inks containing at least 25% Joncryl 67 and 75% polyester polymer (weight percent of total polymer solids).

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Polyesters Or Polycarbonates (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (2)

Family

ID=22845207

Family Applications (2)

Family Applications After (1)

Country Status (8)

Cited By (3)

Families Citing this family (29)

Citations (1)

Family Cites Families (17)

• 1988
  • 1988-07-28 US US07/225,520 patent/US4996252A/en not_active Expired - Lifetime
• 1989
  • 1989-07-13 ES ES89420256T patent/ES2059809T3/es not_active Expired - Lifetime
  • 1989-07-13 JP JP1508062A patent/JPH03506048A/ja active Pending
  • 1989-07-13 EP EP89420256A patent/EP0356341B1/de not_active Expired - Lifetime
  • 1989-07-13 AT AT89420256T patent/ATE96829T1/de not_active IP Right Cessation
  • 1989-07-13 WO PCT/US1989/002984 patent/WO1990001048A1/en not_active Application Discontinuation
  • 1989-07-13 EP EP19890908573 patent/EP0426728A1/de active Pending
  • 1989-07-13 KR KR1019900700664A patent/KR970011099B1/ko active IP Right Grant
  • 1989-07-13 DE DE68910433T patent/DE68910433T2/de not_active Expired - Fee Related

Patent Citations (1)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events